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Advances in C-H Bond Activation and Functionalization

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (31 October 2020) | Viewed by 15074

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Special Issue Editor

Dr. Noel Nebra

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Guest Editor

Laboratoire Hétérochimie Fondamentale et Appliquée, Université Paul Sabatier / CNRS UMR 5069, 118 Route de Narbonne, 31062 Toulouse, France
Interests: organometallic chemistry; main group elements; fluorine chemistry; reaction mechanisms; trifluoromethylations; high-valent species; isolation and detection of reactive intermediates

Special Issue Information

Dear Colleagues,

Organometallic compounds play a pivotal role in modern life since they are decisively involved in a plethora of industrial applications. In this sense, drug discovery, agrochemical invention, small molecule functionalization and material science are drastically impacted by the most recent advancements in organometallic chemistry. With no doubt, cross-coupling reactions are considered amongst the most remarkable findings mediated by Transition Metal (TM) species within the last decades. Accordingly, the pioneering work by Suzuki, Heck and Negishi was recognized with the Nobel Prize in 2010. Further improvements within the field include C-Heteroatom bond formations (i.e. Ullmann type coupling, Buchwald-Hartwig reaction, Chan-Lam-Evans coupling,…) or the more challenging fluorination and perfluorinations of aromatics.

The use of TM-catalyzed C-H bond activation strategies to build C-C and C-Heteroatom functionalities represents an appealing and straightforward alternative precluding previous functionalization steps, isolation of intermediates and metallic waste production. Typically enabled by second and third row TM complexes, a major concern on C-H bond functionalization chemistry deals with the commonly observed lack of selectivity. Growing interest is now focused on novel reactivity patterns and selectivity improvement merging abundant and affordable first row TMs and a substrate/ligand design strategy. Inspired by nature, metalloenzymes allows for a myriad of transformations including C-H bond oxidations. Nowadays, original C-H bond activation and functionalization pathways enabled by photoredox catalysis are emerging research arenas as well.

This Special Issue will collect different aspects regarding the most recent advances in arene and alkane modification through C-H bond activation processes. We thus invite either original research articles or comprehensive reviews dealing with the aforementioned fields including organic synthesis, ligand design conception, TM, metalloenzymes and photoredox catalysis. In depth mechanistic investigation and fundamental studies of C-H bond activations are also welcomed in the current Special Issue.

Dr. Noel Nebra
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

C-H bond activation
Organometallics
Ligand design strategy
First row transition metals
Photoredox catalysis
Metalloenzymes
Mechanism elucidation and reaction intermediates

Published Papers (4 papers)

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Research

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13 pages, 4766 KiB

Open AccessArticle

Selective Oxidation of Ethane to Acetic Acid Catalyzed by a C-Scorpionate Iron(II) Complex: A Homogeneous vs. Heterogeneous Comparison

by Inês A. S. Matias, Ana P. C. Ribeiro and Luísa M. D. R. S. Martins

Molecules 2020, 25(23), 5642; https://doi.org/10.3390/molecules25235642 - 30 Nov 2020

Cited by 6 | Viewed by 2076

Abstract

The direct, one-pot oxidation of ethane to acetic acid was, for the first time, performed using a C-scorpionate complex anchored onto a magnetic core-shell support, the Fe₃O₄/TiO₂/[FeCl₂{κ³-HC(pz)₃}] composite. This catalytic system, where the magnetic catalyst is easily recovered and reused, is highly selective to the acetic acid synthesis. The performed green metrics calculations highlight the “greeness” of the new ethane oxidation procedure. Full article

(This article belongs to the Special Issue Advances in C-H Bond Activation and Functionalization)

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Review

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67 pages, 24314 KiB

Open AccessReview

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

by Hamid Azizollahi and José-Antonio García-López

Molecules 2020, 25(24), 5900; https://doi.org/10.3390/molecules25245900 - 13 Dec 2020

Cited by 16 | Viewed by 4864

Abstract

The functionalization of C–H bonds has become a major thread of research in organic synthesis that can be assessed from different angles, for instance depending on the type of catalyst employed or the overall transformation that is carried out. This review compiles recent progress in synthetic methodology that merges the functionalization of C–H bonds along with the cleavage of C–C bonds, either in intra- or intermolecular fashion. The manuscript is organized in two main sections according to the type of substrate in which the cleavage of the C–C bond takes place, basically attending to the scission of strained or unstrained C–C bonds. Furthermore, the related research works have been grouped on the basis of the mechanistic aspects of the different transformations that are carried out, i.e.,: (a) classic transition metal catalysis where organometallic intermediates are involved; (b) processes occurring via radical intermediates generated through the use of radical initiators or photochemically; and (c) reactions that are catalyzed or mediated by suitable Lewis or Brønsted acid or bases, where molecular rearrangements take place. Thus, throughout the review a wide range of synthetic approaches show that the combination of C–H and C–C cleavage in single synthetic operations can serve as a platform to achieve complex molecular skeletons in a straightforward manner, among them interesting carbo- and heterocyclic scaffolds. Full article

(This article belongs to the Special Issue Advances in C-H Bond Activation and Functionalization)

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40 pages, 30074 KiB

Open AccessReview

Recent Advances in Rapid Synthesis of Non-proteinogenic Amino Acids from Proteinogenic Amino Acids Derivatives via Direct Photo-Mediated C–H Functionalization

by Zhenbo Yuan, Xuanzhong Liu, Changmei Liu, Yan Zhang and Yijian Rao

Molecules 2020, 25(22), 5270; https://doi.org/10.3390/molecules25225270 - 12 Nov 2020

Cited by 13 | Viewed by 3886

Abstract

Non-proteinogenic amino acids have attracted tremendous interest for their essential applications in the realm of biology and chemistry. Recently, rising C–H functionalization has been considered an alternative powerful method for the direct synthesis of non-proteinogenic amino acids. Meanwhile, photochemistry has become popular for its predominant advantages of mild conditions and conservation of energy. Therefore, C–H functionalization and photochemistry have been merged to synthesize diverse non-proteinogenic amino acids in a mild and environmentally friendly way. In this review, the recent developments in the photo-mediated C–H functionalization of proteinogenic amino acids derivatives for the rapid synthesis of versatile non-proteinogenic amino acids are presented. Moreover, postulated mechanisms are also described wherever needed. Full article

(This article belongs to the Special Issue Advances in C-H Bond Activation and Functionalization)

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23 pages, 4710 KiB

Open AccessReview

Fatty Acid Allosteric Regulation of C-H Activation in Plant and Animal Lipoxygenases

by Adam R. Offenbacher and Theodore R. Holman

Molecules 2020, 25(15), 3374; https://doi.org/10.3390/molecules25153374 - 24 Jul 2020

Cited by 17 | Viewed by 3399

Abstract

Lipoxygenases (LOXs) catalyze the (per) oxidation of fatty acids that serve as important mediators for cell signaling and inflammation. These reactions are initiated by a C-H activation step that is allosterically regulated in plant and animal enzymes. LOXs from higher eukaryotes are equipped with an N-terminal PLAT (Polycystin-1, Lipoxygenase, Alpha-Toxin) domain that has been implicated to bind to small molecule allosteric effectors, which in turn modulate substrate specificity and the rate-limiting steps of catalysis. Herein, the kinetic and structural evidence that describes the allosteric regulation of plant and animal lipoxygenase chemistry by fatty acids and their derivatives are summarized. Full article

(This article belongs to the Special Issue Advances in C-H Bond Activation and Functionalization)

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